Aerosol and Air Quality Research, 15: 5871, 2015

Copyright Taiwan Association for Aerosol Research

ISSN: 1680-8584 print / 2071-1409 online
doi: 10.4209/aaqr.2013.08.0270

Bulk Level to Individual Particle Level Chemical Composition of Atmospheric

Dust Aerosols (PM5) over a Semi-Arid Urban Zone of Western India (Rajasthan)
Rajesh Agnihotri1*, Sumit K. Mishra1,2, Pawan Yadav1, Sukhvir Singh1, Rashmi1,
M.V.S.N. Prasad1, C. Sharma1, Bhuwan Chandra Arya1
1

CSIR-National Physical Laboratory, Dr. K.S. Kishnan Marg, New Delhi, 110012, India
Climate, Atmospheric Science & Physical Oceanography Division, Scripps Institution of Oceanography, University of
California San Diego, La Jolla, CA 92093-0234, USA

ABSTRACT
Mineral dust particles in the lower atmosphere may significantly influence radiative and optical budgets, along with the
net chemical balance, through their interactions with ambient chemicals. Their ability to absorb/scatter incoming radiation
strongly depends on their chemical composition (i.e., distribution of major crustal elements), but as yet there is no adequate
regional database with regard to this for the Indian region. To create a regional database of background mineral dust from
a semi-arid zone of western India, we measured the chemical composition of ambient particles (with aerodynamic
diameter 5 m; PM5), collected from seven locations of Jaipur city (in the vicinity of Thar Desert; Rajasthan) at varying
altitudes, during late-winter of 2012. The chemical compositions of the sampled particles at both bulk and individual levels
were measured using X-ray fluorescence (XRF) and Scanning Electron Microscope equipped with Energy Dispersive Xray (SEM-EDX) techniques, respectively. Significant differences in chemical compositions were observed among the
seven sites, yet the bulk chemical compositions of the particles were broadly consistent with those of individual particles.
Average elemental ratios of Mg/Al, Si/Al, K/Al, Ca/Al, Mn/Al, Fe/Al were found to be 0.44 0.22, 1.96 0.90, 0.65
0.22, 1.52 0.40, 0.84 and 1.54 1.67, respectively. We also estimated the complex refractive index (RIs at 550 nm
wavelength) for the studied sites, yielding an average n and k (the real and imaginary parts of RI, respectively) of (1.56
0.03) + (6.5 4.6) 103i, with the aerosols collected from Kukas Hill area (27.02N, 75.85E) having the highest iron
(Fe) mass fraction (~43%). Non-crustal elements e.g., Cu, S, C, Ag and Pb were found only in aerosols over the main city
Birla Temple (Jaipur) at ground level (26.89N, 75.81E).
Keywords: PM5; Mineral dust aerosols; Rajasthan; Chemical composition; Refractive index.

INTRODUCTION
About 50% of the global production of tropospheric
aerosols consists of mineral aerosol particles, originating
mainly from the deserts and their borders (Andrea et al.,
1986). Quantitatively ~10003000 Tg of mineral dust particles
are injected into the troposphere annually (Andreae, 1995).
Introduced mineral dust particles into the lower atmosphere
are capable of traveling long distances before their eventual
dry/wet deposition (Husar et al., 2001; Fairlie et al., 2007).
Mineral dust particles originating from the desert regions can
potentially influence heterogeneous atmospheric chemistry
and thus regional as well as global climate (Ravishankara,
1997; Buseck and Posfai, 1999; Tegen et al., 2003; Xu et al.,

Corresponding author.
Tel.: +91-11-4560-9416; Fax: +91-11-4560-2263
E-mail address: rajagni9@@gmail.com

2004; Bauer et al., 2007). Besides, they can scatter/absorb

incoming solar radiation influencing net radiative/optical
forcing of the region (Sokolik and Toon, 1996, 1999; Sokolik
et al., 2001; Mishra et al., 2008a, b, 2012). There are
considerable uncertainties in the regional radiative/optical
forcings, mainly due to strong variability of the atmospheric
dust burden and the lack of chemical composition data
(Kandler et al., 2007). Many modeling studies also point to
the uncertainties accountable to the lack of physico-chemical
properties of mineral dust, as a limiting factor in estimating
their climatic impact (e.g., Myhre and Stordal, 2001). Studies
dealing with these aspects suggest that the climate forcing
and heterogeneous atmospheric chemistry of individual
mineral dust particles strongly depend on their mineral
components (e.g., calcite, dolomite, and hematite) (Krueger et
al., 2004; Kelly and Wexler, 2005). As far as the Indian
region is concerned, it has been shown that the chemical
composition of mineral dust especially hematite fraction can
significantly influence optical properties (such as single
scattering albedo, asymmetry factor) by Mishra and Tripathi

Agnihotri et al., Aerosol and Air Quality Research, 15: 5871, 2015

(2008a). Subsequently, Mishra et al. (2008b) also assessed

the effect of mineral dust particle composition and shape on
radiative forcing of dust aerosols. Recently Mishra et al.
(2012) further studied effects of particle shape, hematite
content and semi-external mixing with carbonaceous species.
The Thar Desert of Rajasthan is considered as the biggest
regional dust source in India, from where large amount of
dust originates and subsequently dispersed to the heavily
populated Indo-Gangetic plains (IGP) in spring intermonsoon season, and finally reaches all the way up to the
India Ocean (through adjacent seas Arabian Sea and Bay
of Bengal). With rapid development and urbanization of
the state, mineral dust can get mixed with local pollution
and that can significantly alter their optical properties (Mishra
et al., 2012). State capital of Rajasthan, Jaipur (26.89N,
75.81E), also popularly known as Pink city is surrounded
by several old forts situated on the medium scale barren
mountains such as Amber, Jaigarh, Nahargarh of varying
altitude ranging from 5001000 m from ground level.
Besides these Kukas hills (~500800 m from ground) are
situated on outer Jaipur along the Delhi-Jaipur Highway
(NH-8). Additionally, The Rajasthan state is known for its
rich mineral resources especially marble and granite rocks.
Makarana (~110 km west of Jaipur) is known as active
limestone mining area, famous for its Makarana marbles.
Hence aerosol particles over this semi-arid urban location
of Jaipur city could be influenced by regional topography/
geology and emissions due to ongoing anthropogenic
activities (such as rock mining, vehicular pollution, road/
building constructions etc.). The chosen sampling time (lateFebruary) of this expedition is expected to provide local
scale variability in aerosol composition for which regional
detailed chemical and physical database of ambient aerosols
is highly sparse. To create such database at bulk as well as
individual particle level, we collected atmospheric aerosols
(particle of aerodynamic diameter < 5 m (PM5) and few
bulk particles as well (total suspended particulate; TSPs))
from six selected locations of Jaipur situated at different
altitudes and one aerosol sample from the Makarana mining
area. We collected ambient aerosol samples from the five
heighted places around the Jaipur city to capture regionally
representative dataset. Two locales (i) Birla Temple Jaipur
and (ii) Makarana mining area, are chosen where one can
expect aerosols to be influenced by local scale activities
such as urban vehicular pollution and rock mining and cutting
activities, respectively. Purpose of covering these locales
was to capture regional heterogeneity in the measured data.
PM5 size ambient particles were chosen for sampling
because studies by Negi et al. (1996, 2002) that have
shown size of mineral dust particles in general vary (from
aerodynamic diameter ~5 to ~50 m) and particles with size
15 m (PM5) were found to be embedded on the surface
of the large particles. Also due to their high residence time,
interact more with the incoming radiation compared to
large particles (Mishra and Tripathi, 2008). Although the
presence of larger particles near the source cannot be ignored,
their contribution to the total global annual averaged dust
load is negligible (Miller et al., 2006). The modeling study
by Miller et al. (2006) suggests that the total global annual

59

averaged dust load in the atmosphere is mainly due to dust

particles of aerodynamic radii < 10 m with those of radii
12 m making the largest contribution to it. In addition,
PM5 size particles of mineral dust are more likely to
undergo long range transportation via prevailing winds.
Bulk chemical compositions of collected mineral dust
particles were assessed using X-ray Fluorescence (XRF)
technique, whereas selected individual particles from each
site were imaged and analyzed for their chemical composition
using Scanning electron microscope coupled with Energy
dispersive X-ray (SEM-EDX) facility of National Physical
Laboratory (NPL-New Delhi).
To the best of our knowledge, this is a first report from a
semi-arid urban zone of western India comprising ambient
aerosol particle composition both at bulk as well as
individual level. Obtained database of background mineral
dust aerosols originating from the semi-arid zone (in the
vicinity of the Thar Desert) thus may prove to be highly
helpful in ascertaining regional optical and radiative
properties of ambient aerosols.
STUDY AREA AND METHODOLOGY
As mentioned before, ambient aerosol particles of size
fraction PM5 were collected from six sites of Jaipur of
varying altitude plus one site representing active mining
area i.e., Makarana (~120 km west of Jaipur). Details of all
the collection sites and environmental conditions during
sampling are summarized in Table 1. Fig. 1 shows the
sampling locations, picture of installed apparatus used for
particle sampling and key atmospheric backgrounds
photographed from sampling locations. All the aerosol
samples were collected on 37 mm Teflon and precombusted quartz filters as collection substrates installed
on low-volume air samplers APM-801 (Envirotech). The
air flow rates were generally kept at 11.5 L/min (LPM)
(Table 1). A few total suspended particulate matter (TSPM)
samples mainly from Kukas area were collected on 25
mm filters. Mineral dust particles are generally of relatively
coarser size aerosols, PM5 size fraction of these aerosols
should ideally belong to size fraction that is capable of
reaching relatively higher altitude and getting dispersed in the
atmosphere via long range transport. For particle imaging
and analyzing morphological parameters small square
plates of tin (of size 1 1 mm2; thickness ~0.1 mm) were
placed on Teflon filters. Before collection exposure sides
of tin plates were marked and after collection these plates
were carefully stored in small micro-biological specimen
tubes and labeled for SEM-EDX analyses in NPL. Details
on dust morphological characterization and morphological
parameters have been discussed in a companion paper
(Mishra et al., submitted manuscript). Collection-substrates
(Teflon filters) were weighed before and after sampling
using a METLER balance to calculate mass concentrations
of particles. Bulk chemical composition of PM5 particles
collected over all the sites were analyzed non-destructively
using XRF technique. Measurements were carried out
using Rigaku ZSX Primus wavelength Dispersive XRF
spectrometer. The XRF-spectrometer has an Rh-target,

E
E
W
N
1.5
1.5
1.5
1.5
360
150
240
240
10
800
50
10
75.892
75.919
74.714
75.816
22-02-2012
22-02-2012
23-02-2012
25-02-2012
Kukas Near NH-8
Kukas Hill
Makarana Mining area
Birla Temple Jaipur

27.036
27.027
27.042
26.893

75.851
75.844
75.816
19-02-2012
20-02-2012
21-02-2012
Lower Jaigarh Fort
Jaigarh Fort
Nahargarh Fort

26.984
26.982
26.94

55.6
44.4
500.0
222.2

Sunny
Partly sunny
Bright Sunny followed
mild dust storm
Clear sky
Sunny
Mostly sunny
Sunny
34.7
250.0
185.2
1.2
1.0
1.5
240
360
360

Wind
direction
Weather
[PM5]
g/m3
Flow rate
(LPM)
Total time
(min)

Approx. height
of sampling
(MAGL)
600
1000
800
Longitude
Latitude
Date of
collection
Site Name

Table 1. Details of sampling locations, collection parameters and environmental conditions during the field campaign of Jaipur city.

N-NW
W-SW
W

Agnihotri et al., Aerosol and Air Quality Research, 15: 5871, 2015

60

end-window, 4 kW, sealed X-ray tube as the excitation

source and scintillation counter (SC) for heavy elements
and flow proportional counter (F-PC) for light elements as
the detectors. Chemical composition of some of the
selected individual particles collected on tin substrate were
studied using a SEM (ZEISS EVO MA-10) equipped with
an EDX spectrometer (Oxford Link ISIS 300). SEM is
capable of resolving 3 nm size particle at 30 KV accelerating
voltage. Energy dispersive spectrometer attached to the SEM
can identify the elements having atomic numbers of the
elements from beryllium (Be) to uranium (U) with a spectral
resolution of 133 eV.
WIND TRAJECTORIES
From the known overall climatology of the Jaipur area,
it is clear that during the month of February typical wind
speeds vary from 0 to 4 m/s (calm to gentle breeze), rarely
exceeding 8 m/s (moderate breeze) at ground level. Hence,
this is probably an ideal time to capture the physical and
chemical characteristics of background mineral dust of
local origin. Winds are blowing most often from the west,
occasionally from the east and south west. For shorter time
intervals, winds are also found to be blowing from the
southeast and north (source: http://weatherspark.com/aver
ages/33936/2/Jaipur-Rajasthan-India). In order to inspect a
more realistic view for our sampling period i.e., 1925
February, 2012, seven days backward trajectory analyses
were carried out to identify the transport pattern of the air
masses arriving at 500 m above ground level using HYSPLIT
(Hybrid Single-Particle Lagrangian Integrated Trajectory)
[source: http://ready.arl.noaa.gov/hysplit-bin/trajasrc.pl]. Fig 2
illustrates the typical air mass flows on different days of
sampling period i.e., 1925 February, 2012. As all the
samples sites are not spatially very far from each other
(Table 1), we have chosen single latitude and longitude
position (26.94N, 75.82E) to compute backward trajectories,
with the assumption that air masses over this location is
representing a common scenario for all the studied sites.
Fig. 2 shows winds directions prevalent during the sampling
period i.e., 1925 February. On 19-February, winds were
found to be originating from north-northwest, while next
day winds were also from southwest. On 21 February, winds
were found to be blowing from western side, next day
exactly opposite scenario was observed i.e., winds seem to
be originating from east, northeast side. On 23 and 25
February, winds were mainly blowing from north-northwest
(Fig. 2). Thus, backward wind trajectories computed using
HYSPLIT model corroborates the fact during the month of
February; winds over the Jaipur city are not coming from
any specific direction and local erosion can dominate
atmospheric mineral dust particles in this dry period. This was
the reason why late February was chosen for conducting this
experiment.
RESULTS AND DISCUSSION
Results are presented in the following sub-sections.
Elemental compositions of sampled PM5 particles at bulk

Agnihotri et al., Aerosol and Air Quality Research, 15: 5871, 2015

61

Fig. 1. Site locations of collected atmospheric dust samples from hill regions of Jaipur city Rajasthan (India). Inserted panels
show typical sites, micro-volume sampler and sampler assembly. The base map of site location is adapted from Google earth.

Fig. 2. Seven day back trajectory analyses (using NOAA HYbrid Single -Particle Lagrangian Integrated Trajectory
(HYSPLIT) Model accessed via website (http://ready.arl.noaa.gov/hysplit-bin/trajasrc.pl) for the sampling dates (Table 1)
in order to ascertain the long-range transport of air masses.

62

Agnihotri et al., Aerosol and Air Quality Research, 15: 5871, 2015

level (determined using XRF spectrometer) are discussed

first, followed by selected individual particle chemical
compositions (determined by SEM-EDX) along with particle
images. Salient features of elemental composition of ambient
particles over Jaipur are discussed in the context of published
literature, thereafter.
Elemental Composition of PM5 Particles at Bulk Level
Mass concentrations of ambient PM5 size particles over
Jaipur show large variations. Minimum PM5 mass
concentration (34.7 g/m3) was found over lower Jaigarh,
near Amber fort (Table 1), whereas maximum PM5 mass
concentration (499.8 g/m3) was found near Makarana
mining area of Rajasthan) (Fig. 3(a)). Major elements found
in PM5 particles are Si, Al, Cr, Fe, Mg, K, Ca, Mn and S,
variability in their respective mass concentrations is shown
in Fig. 3(b). In general, common major crustal elements found
in atmospheric particles over all the sites are Si, Al, Fe,
however, maximum variability was shown by Fe (Fig. 3(b)).
Elemental mass fractions showed considerable variability
for key crustal elements e.g., Ca and Fe and K (Table 2);
average Element/Al ratios found in this study were compared
with those of average upper continental crust (Ruidnick
and Gao, 2003) and Saharan mineral dust (Formenti et al.,
2003). Table 2 reveals mineral dust particles sampled in
this study showing significantly higher values of Ca/Al,
Fe/Al and K/Al ratios. Using measured elemental data, we
estimated respective elemental oxides (Table 3). Using
elemental oxide data, we also estimated the portion of total
mass accounted by elemental oxides of major crustal elements
viz. Si, Al., Ca, Mg, K and Fe. Total mass accountable by
crustal elements viz. Si, Al, Ca, Mg, K and Fe for lower
Jaigarh, Nahargarh fort, Kukas highway NH-8, Jaigarh fort
and Birla temple area are ~81%, 45%, 40%, 30% and 16%
respectively. Maximal mass fraction accountable by crustal
elemental oxides appears to be from aerosols over Kukas
hill area (~99%) due to higher Fe content. Using elemental
oxide data it is possible to estimate spectral variation of
refractive indices (RIs), which are vital data input for
estimation of optical properties. Except for the Makarana
area, Fe was found to be abundant at all the studied sites
with highest mass fractions of Fe found in aerosol particles
over Kukas hill area (Table 2). We also note that higher Cr
concentrations found in ambient PM5 particles over almost
all the sampled sites (Table 2; Fig. 3(b)).
In addition, we also determined enrichment factors of
elements using Si as a reference crustal element and using
mean elemental ratio with respect to Si in upper continental
crust (Rudnick and Gao, 2003). Maximum enrichment factors
were obtained for Fe especially over Kukas hill and Kukas
NH-8 highway. Following Fe, Ca and K were also found
to be enriched in PM5 particles over Jaigarh, Nahargarh,
Birla Temple and Makarana mining area (Fig. 3(d)).
Average elemental ratios of Mg/Al, Si/Al, K/Al, Ca/Al,
Mn/Al, Fe/Al of PM5 aerosols (at bulk level) were found to
be 0.44 0.22, 1.96 0.90, 0.65 0.22, 1.52 0.40, 0.84
and 1.54 1.67 respectively. Average Si/Al ratio in ambient
PM5 particles over Jaipur are thus well within the overall
variability of Si/Al ratios of Saharan dust (typical value

Fig. 3. (a) Variability in measured elemental concentrations

in PM5 particles for all sites, as determined by XRF
analyses. (b) Observed elemental ratios with respect to Al
in comparison to respective elemental ratios found in
upper continental crust. (c) Observed enrichment factors of
element with respect to Si.
~2.3; Formenti et al., 2001). The average elemental mass
ratios in the work of Kandler et al. (2007) who sampled
Saharan dust from Spain are 2.14 (Si/Al), 0.20 (K/Al),
0.28 (Ca/Al), and 0.58 (Fe/Al). Noteworthy is the fact that
ambient dust over Jaipur shows higher average K/Al,
Ca/Al and Fe/Al ratios. Higher Ca/Al ratios are consistent
with findings of Tindale and Pease (1999), who reported
Ca rich dust over the Arabian Sea, most likely originated
from the Thar Desert region. Average Ca/Al ratio in bulk

Site Name
Lower Jaigarh Fort
Jaigarh Fort
Nahargarh Fort
Kukas Near NH-8
Kukas Hill
Makarana Mining area
Birla Temple Jaipur

0.50
1.26

1.04
2.06

MgO%

Al2O3%
35.52
5.01
7.03
10.18
16.53
0.76
3.24
SiO2%
34.81
14.79
21.39
19.62
22.19
2.84
5.12

P2O5%
1.45
0.41
0.35

0.88
2.36

2.09
3.80

SO4%

0.47
1.04

2.09
2.14

K2O%

1.18
3.18

4.25
7.90

CaO%

Cr2O3%
4.62
6.79
4.14
27.00
31.87
0.80
0.61

Si%
P%
S%
K%
Ca%
Cr%
16.27
0.63
3.16
6.91
0.18
0.70
1.74
3.04
4.65
10.00
0.15
1.27
1.78
5.64
2.84
9.17
18.48
10.37
21.81
1.33
0.29
0.39
0.84
0.55
2.40
0.79
0.87
2.27
0.42
Si/Al
P/Al
S/Al
K/Al
Ca/Al
Cr/Al
1.00
1.96 0.90
0.05 0.02 0.45 0.20 0.65 0.22
1.52 0.40 1.46 1.20
1
3.82
0.01
0.29
0.31
2.14
0.2
0.28
2.03, 2.21, 2.32 0.012 0.002
0.18, 0.21, 0.24 0.20, 0.36, 0.60
-

Al%
18.80
2.65
3.72
5.39
8.75
0.40
1.72

Table 3. Estimated elemental oxides in weight percentages over all the sites.

Site Name
Mg %
Lower Jaigarh Fort
Jaigarh Fort
0.62
Nahargarh Fort
1.24
Kukas Near NH-8
Kukas Hill
Makarana Mining area
0.30
Birla Temple Jaipur
0.76
Average ratios
Mg/Al
This study
0.44 0.22
Mean upper crust
0.18
Saharan dust sampled from Spain
Saharan dust
-

4.93

MnO2%

Mn%
3.12
Mn/Al
0.84
0.01

2.19

Fe2O3%
11.35
3.32
4.18
10.76
61.21

Fe%
7.94
2.32
2.93
7.53
42.82
1.53
Fe/Al
1.54 1.67
0.48
0.58
0.54, 0.52, 0.54

Table 2. Variability observed in elemental mass fractions and characteristic average Element/Al ratios in the context of average upper continental crust and Saharan mineral
dust.

Agnihotri et al., Aerosol and Air Quality Research, 15: 5871, 2015
63

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Agnihotri et al., Aerosol and Air Quality Research, 15: 5871, 2015

aerosols (TSPM) collected from Ahmedabad (known to

receive mineral dust from the Thar Desert during late winter
FebruaryMarch) varied from 0.75 to 1.25 with a mean
value of 1.04 0.13 (Rastogi and Sarin, 2009). Similarly
higher Ca/Al, K/Al and Fe/Al ratios have been reported in
aerosols over Bay of Bengal during late inter-monsoon
season, when calcareous mineral dust originating from the
Thar Desert is expected to be the major contributor of
crustal elements (Srinivas and Sarin, 2012). Thus observed
elemental ratios especially Ca/Al, K/Al and Fe/Al measured
in this study could be used as representative elemental ratios
of the background mineral dust of this semi-arid zone (in
the vicinity of the Thar Desert). Though individual particle
chemical compositions are presented in the next section, it is
important to mention here that individual particle chemical
compositions measured by SEM-EDX were found to be in
good agreement with bulk level chemical compositions.
Significant enrichment of Fe in ambient particles over
Kukas hill and surrounding region (Kukas NH-8 highway)
is important as Fe is a key element (in the form of mineral
hematite; Fe2O3) for incoming solar (visible) energy
absorption and thus heating the atmosphere (Lafon et al.,
2006). Besides Fe, Cr is also high in ambient PM5 particles
over almost all the sites studied and specifically over
Kukas hill region. Cr/Al ratio show significant variability
with an average value of 1.46 1.2 (Table 2). Though the
Kukas hill area is along the sides of Delhi-Jaipur National
highway (NH-8), an area with a busy vehicular traffic,
however absence of non-crustal elements (e.g., Cu, Ni, Pb,
S, potential indicator of local vehicular emission) disfavors
the possibility of enhanced Fe and Cr due to vehicular
emission. Since the Kukas industrial area is also known for
various other activities such as assembling heavy vehicles
(trucks and buses) which involve welding that may be a
plausible source of extra Fe in local aerosols. To pin point
which type of anthropogenic activity is responsible for
high Fe inventory to ambient aerosol particles, certainly a
more number of samples and data are required to gain
further insights of ambient particle chemistry over Kukas
area. Nonetheless, the observed Fe rich ambient particles
certainly appear to be capable of influencing regional
optical/radiation budgets significantly.
Elemental Composition of Individual Particles
Over all 235 particles were analyzed for estimation of
morphological parameters in this study (Mishra et al.,
submitted manuscript). From which, a total of 25 individual
particles were analyzed by EDX for chemical composition;
from that a total 15 typical individual particles along with
their chemical composition are shown in Figs. 47 (~24
particles per sample). It is true that number of particles
analyzed by EDX should be as high as possible in order to
get better statistical comparison with XRF measured bulk
chemical composition. However it also noteworthy here, that
individual particles were manually selected for imaging and
spot EDX analysis and hence it is a labor intensive and
time consuming work.
Hence, selected individual mineral dust particles from
all the seven sites were imaged and their elemental

compositions were determined using spot-EDX. From this

data, a few representative particle images along with
elemental composition are presented in Figs. 47. Highly
non-spherical particles were found with predominance of
Layered (Ca, Si rich), Angular structures (Si rich) and
Flattened particles over all the sites (Mishra et al.,
submitted manuscript). Most of the particles appear to be
aggregates of different mineralogical composition as
corroborated by their SEM images (Figs. 47). The
elemental data of individual particles (Figs. 47) indicate
that particles contain mainly Si, Al, Ca, Mg, K, and Fe as
crustal elements besides C and O oxides (Table 4). For
almost all the individual particles the sum of all measured
elements including C, N, O (Table 4) add up to ~100,
indicating that estimated elemental distribution nearly
reflects the particles total chemical composition. Particles
from Kukas hill and surrounding area (Kukas highway
NH-8) are Fe rich but poor in Ca, while particles from
Makarana and Birla Temple are Ca rich and Fe poor. From
the Table 4 and Fig. 5, it can be seen that most of the
individual particles also show significant Fe enrichments,
corroborating bulk level measurements (section 4.1) of
higher Fe contents of aerosols over Kukas hill and
surrounding regions.
Few particles also showed presence of S. Na was found
only in minor amount in aerosols over Jaigarh-Nahargarh,
Kukas NH-8 highway, Makarana (Figs. 46); except a crystal
structured particle found over main city Birla Temple
(Jaipur) showed Na in higher amount (~29%) (Fig. 7). Ca,
Mg, Si, Al and Fe were found to be abundant in the majority
of particles. Na, K, S, Na, Cl were also present in a few
particles. Among crustal elements, Ti intriguingly was found
only in two individual particles. Non-crustal elements e.g.,
Cu, Ag and Pb (plausible indicators of anthropogenic
pollution) were found to be abundant only in a very few
individual particles (two particles over Birla Temple and
one from Kukas NH-8 night sample). Presence of S in
particles collected from Makarana, Birla temple Jaigarh
and Nahargarh which showed Ca as a significant crustal
component indicate that Gypsum (CaSO4.2H2O) may be
probable mineral phase of Ca. On the other hand, absence
of S in particles which show Fe as abundant component,
disfavor presence of Fe sulfides or sulfates. Hence, Fe may
be present in form of its oxides such hematite, magnetite.
Fig. 5 shows a few Fe-rich particles from Kukas area. In a
previous study Negi et al. (1996) studied TSPM and its
elemental composition from Mount Abu, Rajasthan (high
altitude region in the vicinity of Thar Desert) and reported
particles with higher Fe contents. Chemical composition
data of individual particles from the Makarana mining area
show significant Ca contents (Fig. 6) as can be expected
being an active lime stone mining area, higher amounts of C
and N oxides indicate significant mixing of carbonaceous
material probably originating from drilling activities. Noncrustal elements which are known to be of anthropogenic
origin were found only in aerosol over Birla Temple e.g.,
significant mass fractions of Cu, Pb, Ag along with S
indicating their presence as sulfides (Fig. 7). Aerosol
particles collected from Birla Temple area also showed higher

Agnihotri et al., Aerosol and Air Quality Research, 15: 5871, 2015

65

Fig. 4. SEM images and chemical compositions of individual mineral dust particles over Jaigarh and Nahargarh forts
(Jaipur, Rajasthan). See text for likely minerals inferred from chemical composition.
C mass fractions possibly owing to local scale urban activities
such vehicular traffic.
Major clastic minerals reported in the eastern Thar Desert
region are quartz, plagioclase, K-feldspar, amphibole, mica
and chlorite (Peterson, 1968). Non-clastic mineral assemblage
however is variable and comprises of both evaporite minerals

and carbonates (Roy et al., 2008). Using measured elemental

composition of individual particles, we assessed probable
mineral phase abundant in aerosols over different sites
following Kandler et al. (2007, 2009) (Table 4). The probable
mineral phases of the background mineral dust sampled in
this study, thus, are consistent with previous studies of

Probable Mineral
phase
Quartz, Plagioclase
Gypsum, carbonates
Gypsum, carbonates
Carbon rich partcile
Hematite, Magentite

1.53

Pb

0.65

61.16

Ag

0.21

2.43

0.16
9.79
0.17
24.3
2.54
0.57
1.44 4.87

Cu
Fe

1.11
0.74
52.8
25.9
2.28
2.31
1.69

0.72
2.16
1.5

3.48

29.2

0.61

0.68
22.75
5.76

2.82

0.46
1.56

1.46
2.66
5.73

1.7

8.54
32.21

1.43
1.59

3.52
11.45
14.92
31.97
0.82
64.24
5.07
6.56
81.1
1.04
27.68
37.17
37.41
8.88
9.84
Jaigarh
Jaigarh
Nahargarh
Nahargarh
Kukas_hill_TSPM
Kukas_hill_TSPM
Kukas Hill_PM5
Kukas NH8_Night_TSPM
Kukas NH8_Night_TSPM
Kukas NH8_Night_PM5
Makarana
Makarana
Birla Temple JP
Birla Temple JP
Birla Temple JP

16.73

55.61
34.73
52.12
37.77
48.86
28.7
32.98
46.3
12.47
49.7
43.42
14.2
33.81
1.76
4.06

4.91
0.28
1.54
0.57

0.2
1.54
1.02
0.17
1.32
0.44
1.14
0.37

6.77
0.2
11.34
10
0.8
18.27
0.6

32.92
11.77
11.86
9.09
30.37
2.04
18.34
26.3

0.61
0.28
0.42

1.25
0.59
0.28

0.55
0.58
0.38

1.38
0.53
4.91
1.05

0.83
33.53
6.55
2.84
0.48
1.67
0.5
1.8
4.4
0.53
5.59
16.43
18.96

Ti
Ca
K
Cl
S
Si
Al
Mg
Na
O
N
C
Site

Table 4. Elemental distribution of studied individual aerosol particles and inferred (most likely) minerals for the measured chemical composition.

Hematite, Magentite
Hematite, Magentite
Carbon rich particle
Hematite, Magentite
Carbon rich partcile
Carbon rich partcile
Carbon rich partcile
Cu rich particle
0.3 Salt rich evaporite

Agnihotri et al., Aerosol and Air Quality Research, 15: 5871, 2015

66

Peterson, (1968) and Negi et al. (1996) as both the studies

indicated presence of quartz (Si rich), hematite (Fe rich)
and carbonates Ca rich minerals.
Relationship between Particle Aspect Ratio and Chemical
Composition
Though detailed morphologies of the studied particles
have been presented in Mishra et al. (submitted manuscript),
we attempt here to examine any relationship between
measured aspect ratios (ARs; from Mishra et al., submitted
manuscript) and measured chemical composition. Si and Al
are the only two such elements which were found to be
abundant in all the samples, and Si/Al ratio varied in a
range 1.96 0.9 (Table 2). Si/Al ratios of six different sites
appear to be positive correlated with the measured mean
Aspect ratios (ARs) of particles (r2 = 0.82; n = 6; Fig.
8(a)). Though total numbers of data point are relative small
for a statistically sound relationship, yet we have attempted
to understand plausible causes for such a relationship. The
Si/Al ratios are mainly controlled by the relative proportion
of quartz and clay and, thus, depend upon proportions of
coarse and fine mode particles. Lafon et al. (2006) have
found different Si/Al ratios for different impactor stages
representing fine and coarse modes. Higher Si/Al ratios of
particles therefore are indicative of higher proportion of
coarse mode faction containing more quartz (Si rich) in
ambient aerosol particles, while lower Si/Al ratios are
indicative of higher fine mode fraction (clay fraction enriched
in Al). A positive correlation between Si/Al ratio and ARs of
particles is probably indicating that particles having higher
coarse mode fraction are also more of non-spherical in
nature, compared to particles with the lower Si/Al ratio,
while the relatively higher fine size fraction are closer to
spherical shapes. This observation thus indicates that how
abundances of crustal elements could be related to physical
properties of the particles.
Spatial Variability of Refractive Index of Mineral Dust
Particles over Jaipur
The dust aerosols are composite mixtures of different
minerals. Chemical composition of dust aerosols is thus an
important factor for estimating optical parameters such as
their complex refractive indices. Using elemental oxide
data (Table 2), considering all Fe to be present as hematite
of density 5.3 gm/cc and density of mineral dust to be 2.65
gm/cc (Lee et al., 2009), we computed volume fractions of
hematite in dust aerosols over six sites. Except Kukas hill
area which showed very high Fe contents, average volume
fraction of hematite is estimated as 3.18 1.94, which
agrees well with the estimated hematite content (< 4%
Fe2O3) over Thar Desert (Mishra and Tripathy, 2008a).
Using these volume fractions of hematite we then
computed real and imaginary parts of refractive index (at
550 nm) over six sites of the Jaipur city (Fig. 8(b)). Refractive
index (real and imaginary) of mineral dust has been calculated
using Bruggmans effective medium mixing rule (Bohren and
Huffman, 1998) at 550 nm following the approach adopted
and discussed earlier by Mishra and Tripathi (2008a). The
estimated hematite percentage is the major input in governing

Agnihotri et al., Aerosol and Air Quality Research, 15: 5871, 2015

67

Fig. 5. SEM images and chemical compositions of individual mineral dust particles over Kukas hill and Kukas highway
(Delhi-Jaipur).
the refractive indices. The details for the calculation of indices
have been discussed in the companion paper by Mishra et al.
(submitted manuscript), where the sensitivity of mineral dust
optics with respect to its morphology and mineralogy has
been discussed. Except for Kukas hill area, estimates of
real and imaginary parts of refractive index, i.e., average n
and k for all the other sites vary in a relatively narrow
range (1.56 0.03) + (6.5 4.6) 103i. For the Saharan
area with the mean value RI550nm is reported to be as 1.58 +
1.1 103i , whereas the global mean RI550nm for global
mineral dust (based on FAO/UNESCO Digital Soil Map of
the World) is reported to be (1.59 0.02) + (1.2 0.5) 103i

(Smith and Grainger, 2009). Real parts n of RI estimated

for Indian region agrees well with global/Saharan mineral
dust data while imaginary parts k shows higher values.
Claquin et al. (1998) reported that the imaginary part of
refractive index k is significantly influenced by natural
chemical composition/variability of particles which can
lead to significant variations (as high as ~40%) in aerosol
forcing calculations, underscoring the importance of regionspecific data for validity of such estimations. As far as Kukas
hill region is concerned, it appears that more samples and
representative data are required to ascertain physico-chemical
properties of aerosols over this region.

68

Agnihotri et al., Aerosol and Air Quality Research, 15: 5871, 2015

Fig. 6. SEM images and chemical compositions of individual mineral dust particles from Makarana mining area (Rajasthan,
India).

Fig. 7. SEM images and chemical compositions of individual mineral dust particles over the main city (Birla Temple; Jaipur).
SUMMARY
Most of the ambient particles were found to be highly nonspherical in shape (Mishra et al., 2014, submitted manuscript)
and composed of crustal elements e.g., Si, Al, K, Mg, Ca
and Fe. Ambient particles over Kukas Hill area showed

highest iron (Fe) mass fraction (~43%). Chromium (Cr)

was also found to be abundant in the sampled mineral dust
particles over almost all the sites. It is noteworthy, because
Cr enriched dust particles over Indian plains are generally
thought to be of Arabic (Oman) origin. Non-crustal elements
were found only over the main city (Birla Temple, Jaipur)

Agnihotri et al., Aerosol and Air Quality Research, 15: 5871, 2015

69

2006; Mishra and Tripathy, 2008b).

This is a first step of the our ongoing detailed physicochemical characterization of atmospheric particles for
generating region-specific database of ambient aerosols
from the vicinity of the Thar Desert region, that could greatly
help better estimation of optical constants of mineral dust
(governing optical/radiative properties) and characterizing
long range transport of dust aerosols all the way up to
northern Indian Ocean through Indo-Gangetic plains.
ACKNOWLEDGEMENTS
The authors are thankful to Director NPL, Prof. R.C.
Budhani for facilities used and his consistent support to the
ongoing work. We also acknowledge Google earth map
website and the NOAA Air Resources Laboratory (ARL)
for the provision of the HYSPLIT transport and dispersion
model and the READY website used in this study. Authors
also acknowledge CSIR Network Project AIM_IGPHim
(PSC-0112) for the financial support and constructive
comments from two anonymous reviewers.
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Fig. 8. (a) Inter-relationship between aspect ratio of particles
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71

Received for review, September 9, 2013

Revised, February 6, 2014
Accepted, April 20, 2014